US3862965A - Shaped washing agents based on synthetic tensides - Google Patents

Shaped washing agents based on synthetic tensides Download PDF

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US3862965A
US3862965A US306014A US30601472A US3862965A US 3862965 A US3862965 A US 3862965A US 306014 A US306014 A US 306014A US 30601472 A US30601472 A US 30601472A US 3862965 A US3862965 A US 3862965A
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acids
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Lothar Werner
Werner Schneider
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to BE756790D priority Critical patent/BE756790A/xx
Priority to DE19691949562 priority patent/DE1949562B2/de
Priority to NL7013063.A priority patent/NL164602C/xx
Priority to FR707035096A priority patent/FR2064076B1/fr
Priority to AT884070A priority patent/AT301726B/de
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Priority to US306014A priority patent/US3862965A/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear
    • C11D3/2013—Monohydric alcohols linear fatty or with at least 8 carbon atoms in the alkyl chain
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols

Definitions

  • ABSTRACT Shaped washing agents based on synthetic detergents having a composition consisting essentially of (A) from to 85% by weight of a tenside mixture consisting essentially of 1) from to 100% by weight of the tenside mixture of a sulfonate mixture consisting essentially of (a) from 10% to by weight of the sulfonate mixture of a water-soluble salt of a monoester of a sulfodicarboxylic acid selected from the group consisting of sulfoalkanedioic acids having 3 to 8 carbon atoms and sulfobenzenedicarboxylic acids, monoesterified with aliphatic alcohols having 8 to 18 carbon atoms and (b) from 20% to by weight of the sulfonate mixture of a water-soluble salt of an olefin sulfonate having 10 to 18 carbon atoms, and (2) from O to 30% by weight of the tenside mixture
  • Cakes of soap have the ability to absorb large amounts of water in contact with it, and, thereby, first form a still solid gel. If one washes with such a soap, swollen on a part of the surface, the soap substance rubs off quicker at the swollen areas than at the nonswollen ones, so that the desired foam formation occurs quicker than usual. No loss of soap occurs in this. Washing agent cakes based on the named synthetic tensides behave completely differently. In them the area in which the swollen material adheres solidly to the residual piece is much smaller. In most cases, on the surface of the pieces a smeary mass is formed, which rubs off immediately in washing with such a cake and produces a much higher tenside concentration than would be required for the desired foam formation. For this reason greater material losses occur.
  • a further disadvantage of the known washing agent cakes based on synthetic tensides lies in the strong degreasing of the skin. After washing with them, the disagreeable sensation of a dried-out skin remains.
  • washing agent cakes based on synthetic tensides can indeed be improved by incorporation of waterinsoluble soap cake builders, but even these improved cakes do not satisfy the requirements for a satisfactory washing agent cake.
  • An object of the present invention is the development of a shaped washing agent composition based on synthetic tensides which overcomes the drawbacks mentioned above and can be utilized in place of hand soap cakes.
  • Another object of the invention is the development of shaped washing agents based on synthetic detergents having a composition consisting essentially of (A) from 50 percent to 85 percent by weight of a tenside mixture consisting essentially of (1) from to 100% by weight of the tenside mixture of a sulfonate mixture consisting essentially of (a) from 10% to by weight of the sulfonate mixture of a water-soluble salt of a monoester ofa sulfodicarboxylic acid selected from the group consisting of sulfoalkanedioic acids having 3 to 8 carbon atoms and sulfobenzenedicarboxylic acids, monoesterified with aliphatic alcohols having 8 to 18 carbon atoms and (b) from 20% to 90% by weight of the sulfonate mixture ofa water-soluble salt of an olefin sulfonate having 10 to 18 carbon atoms, and (2) from 0 to 30% by weight of the tenside mixture of the other tensides selected from
  • the invention relates to shaped washing agents based on synthetic tensides, which do not have the above described disadvantages.
  • the shaped washing agents of the invention are characterized by the following composition:
  • a tenside mixture composed of:
  • the other tensides can be anionic, amphoteric, or nonionic.
  • the shaped washing agents of the invention in addition to containing ingredients customary in such products, such as superfatting agents, can contain impurities, originating from the tensides, etc. llnsofar as the below more extensively described water-insoluble superfatting agents (particularly fatty acids and fatty alcohols) are present as solids at temperatures of 30C, and preferably of 40C, they act as builders and belong to the other customary builder materials in the frame of the above recipe.
  • the above-defined surface-active sulfodicarboxylic acid monoesters are known and are accessible by various ways.
  • Monoesters of aliphatic sulfodicarboxylic acids with 4 to 8 carbon atoms such as sulfoalkanedioic acids having 4 to 8 carbon atoms, such as sulfoalkanedioic acids having 4 to 8 carbon atoms, are, for example, obtained by bisulfite addition to the corresponding monoesters of unsaturated dicarboxylic acids.
  • sulfodicarboxylic acid monoesters can, however, be
  • the monoester of the sulfophthalic acid is obtained by treating of phthalic acid monoesters with saturated alcohols with appropriate sulfonating agents.
  • the monoesters of sulfosuccinic acid are preferentially used.
  • the alcohol radicals present in the named compounds are derived from preferably saturated, straightchain, primary aliphatic alcohols such as alkanols with to 18, preferably 12 to 14 carbon atoms.
  • the alcohols can be of synthetic origin or be formed by reduction of synthetic or natural fatty acids.
  • the alcohol mixture obtained from coconut or palm kernel fatty acids, and particularly lauryl alcohol or the mixture oflauryl and myristyl alcohol separated from these fatty alcohol mixtures, are used.
  • Such mixtures can contain fatty alcohols with more than 18 and less than 10, preferably those with 8 carbon atoms, however at least 50, and preferably 70% of the fatty alcohols or fatty alcohol radicals should contain 10 to 16, and particularly 12 to 14, carbon atoms.
  • sulfosuccinic acid monoesters of fatty alcohols derived from coconut or palm kernel fatty acids or the respective C 2 to C fractions are particularly practical importance.
  • the olefin sulfonates utilized in the shaped washing agents of the invention are accessible by sulfonation of straight or branched-chain olefins having a terminal or non-terminal double bond by known procedures.
  • olefin sulfonates utilized in the shaped washing agents of the invention are accessible by sulfonation of straight or branched-chain olefins having a terminal or non-terminal double bond by known procedures.
  • products consist preponderantly of at least 70%, and preferably to more than 85%, of straight-chain olefin sulfonates and of these the sulfonates from straight-chain a-olefins are preferred.
  • olefin sulfonates are known. Of particular practical importance is a procedure in which the olefins are first reacted with gaseous sulfur trioxide in the presence of inert gases. 1 to 2, preferably 1 to 1.5 mols of S0 are used per mol of olefin. An intermediate is formed which gives, after acidic or alkaline hydrolysis at elevated temperatures, the desired sulfonate.
  • sulfonates are chemically nonhomogenous. They consist essentially of a mixture of hydroxyalkane sulfonates, alkene sulfonates and disulfonates. The latter can also possess hydroxyl groups. All the named substances, in regard to the position of the sulfonate group or groups, the hydroxyl group, and the double bond, can be present as mixtures of isomers.
  • the quantitative ratio of hydroxyalkane sulfonates, alkene sulfonates and disulfonates depends to a certain extent upon the conditions of sulfonation and hydrolysis.
  • the working conditions during hydrolysis influence the quantitative proportion of hydroxyalkane sulfonates and alkene sulfonates.
  • the amount of hydroxyalkane sulfonates is reduced in favor/of the alkene sulfonates.
  • Both the sulfodicarboxylic acid monoesters and the olefin sulfonates are obtained, depending upon the selected preparation procedure, in a more or less colored state.
  • the products obtained by sulfonation with gaseous sulfur trioxide are sometimes colored yellowish or brownish, and it may be desirable to bleach these sulfonates.
  • oxidizing bleaching agents such 5.20; o so iu hypgchlorite, are usable- With the use of sodium hypochlorite, slight amounts of sodium chloride remain in the sulfonation product.
  • the sulfonates contain often slight amounts of sodium sulfate.
  • the amount of these neutral salts should, however, be not greater than 15 percent and preferably notgreater than 15 percent with reference to the anhydrous tenside. In many cases, the amount of neutral salts is much less and is for instance 1% to 5%.
  • washing agent cakes are still preserved if limited amounts, up to 30% by weight of the tensides, of other tensides are also present.
  • These tensides can be anionic, nonionic or amphoteric. Most of them contain a preferably straight-chain alkyl radical of 8 to 18, preferably 12 to 16 carbon atoms.
  • the sulfonates and the sulfates are of particular practical importance. To them belong, for example, the alkylbenzene sulfonates, fatty alcohol sulfates, sulfated adducts of 0.5 to 5 mols of ethylene and/or propylene oxide to fatty alcohols, sulfated fatty acid-monoglycerides, mono-fatty acid esters or mono-fatty alcohol ethers of dihydroxypropane-sulfonic acid, fatty acid esters of hydroxyethane-sulfonic acid, fatty acid amides of taurine or methyl taurine, sulfated adducts of l to 5, preferably of 1.5 to 4 mols of ethylene-and/or propylene oxide to alkylphenols, etc.
  • anionic tensides also belong synthetic carboxylates, such as amides of fatty acids and aminocarboxylie acids, particularly the corresponding derivatives of alanine or of sarcosine.
  • soaps also can be present as anionic tensides, although their presence is not compellingly necessary for the improvement ofthe properties of the cake, particularly of the swelling properties toward water. If olefin sulfonates are used for the preparation of the cakes, according to the invention, in the hydrolysis of intermediaries, first formed during the sulfonation, which has been carried out with the use ofexcess alkali, soaps are necessarily formed if free fatty acids are added to the washing agent compositions as superfatting agents.
  • the shaped washing agents can also contain nonionic tensides, but it is recommended, in view of the compactness properties of the shaped washing agents, not to increase their amount above 15 percent, preferably 10 percent by weight of the tenside mixture in the shaped washing agent, particularly if these nonionic tensides are present in an oily or pasty consistency at temperatures below 30C. If one wants to incorporate larger amounts of nonionic tensides, appropriate products should be selected which melt in the range of 4090C.
  • adducts of ethylene oxide to alkylphenols, fatty alcohols, fatty acids, or fatty acid amides are suitable, which, for example, can contain in the molecule 5 to 80, preferably 8 to ethyleneoxide units.
  • the melting points of these products rise on the one hand with the melting point of the starting material, and on the other hand with the amount of added ethylene oxide.
  • mixed adducts of ethylene oxide, on the one hand, and propylene and/or butylene oxide on the other hand,
  • alkylene oxides can be added in any sequence one after the other, or as a mixture
  • Nonionic tensides The products known by their commercial names Pluronics or Tetronics are also usable as nonionic tensides. These products occupy a special place within the scope of the tensides insofar as they do not have to contain an alkyl radical of 8 to 18, preferably 12 to 16 carbon atoms. These alkyl radicals are replaced by polypropylene glycol, or polybutyleneglycol radicals.
  • Such nonionic tensides are obtained from waterinsoluble polypropyleneglycols or from water-insoluble propoxylated lower aliphatic alcohols with l to 8, preferably 3 to 6 carbon atoms and/or from water-insoluble propoxylated alkylene diamines.
  • Monoor dialkylolamides of fatty acids particularly fatty acid monoor diethanolamides belong further to the nonionic tensides.
  • Nonionics, solid at normal temperatures, of the type of ethoxylated fatty alcohols, fatty acids, or alkylphenols with straight-chain C to C alkyl radicals are, for instance, the adducts of 45 mols ofethylene oxide to 1 mol of coconut fatty alcohol; of 20, or 50 mols of ethylene oxide to 1 mol of tallow alcohol; and of 40 mols of ethylene oxide to 1 mol of oleyl alcohol; reaction products of 1 mol of palmitic acid with 40 mols of ethylene oxide or of 1 mol of stearic acid with mols of ethylene oxide as well as of 1 mol of an alkylphenol especially nonylphenol, with 25 to 50 mols of ethylene oxide.
  • the washing agent cakes may also contain amphoteric tensides of which some, particularly the below named compounds with carboxyl groups, possess anti-microbial properties.
  • amphoteric tensides useable, according to the invention, belong, for instance, compounds of the following general formula:
  • R is a higher-molecular-weight alkyl, alkylphenyl, alkylphenoxyalkyl or alkyloxyalkyl radical. particularly a corresponding hydrocarbon radical with 6 to 18, preferably 8 to 14 aliphatic carbon atoms; R, is ethylene or propylene; x is a whole number from 1 to 6; and R is an aliphatic, aliphatic-aromatic or aromatic link with l to 8 carbon atoms, preferably R is alkylene, alkylphenylene, phenylalkylene and phenylene.
  • R has the same meaning as in the preceding formula, R represents an ethyleneor propylene group, R and R are lower alkyl radicals, R is a lower molecular weight aliphatic link such as lower alkylene, and X is an ether oxygen atoms, or the -CONH- group.
  • Examples for such compounds are lauryl-l,3-amidopropyl-dimethyl-aminoacetic acid, lauryl-oxyethyl-di-(hydroxyethyl)-aminopropionic acid, octyl-phenoxy-ethyl-di-(hydroxyetlhyl)-aminoacetic acid, and others.
  • amphoteric tensides useable, according to the invention belong also sulfobetaines, which are, for example, obtained by reacting of dialkyl fatty amines (alkyl radical C to C fatty radical C to C preferably C to C with sultones, particularly with propane sultone and 1,3- or 1,4-butane sultone).
  • dialkyl fatty amines alkyl radical C to C fatty radical C to C preferably C to C with sultones, particularly with propane sultone and 1,3- or 1,4-butane sultone.
  • the amphoteric compounds can be incorporated as inner salts, as salts with the above named alkaline reacting compounds, or as salts with acids.
  • the detergent cakes contain other non-tenside ingredients, customary in shaped detergents, such as super fatting agents, complexing compounds, disinfectants, microbicidal substances, brighteners, buffers for a slightly acidic pH, perfumes, dyes, etc.
  • water-insoluble fatty acids fatty alcohols, mono-, di-, or triglycerides, fatty acid esters, particularly fatty acid esters with fatty alcohols, lanolin, Vaseline, etc. are suitable, preferably melting at temperatures from 30 to C, and particularly 40 to 70C.
  • fatty acid esters particularly fatty acid esters with fatty alcohols, lanolin, Vaseline, etc.
  • esterification products described in German Pat. No.
  • 1,165,574 from equimolecular amounts of a diester of 1 mol of citric acid and two mols of a fatty alcohol with to 20, preferably 12 to 18 carbon atoms and a pentaerythritol-diester of one mol of pentaerythritol and two mols of a fatty acid with 10 to 20, preferably 12 to 18 carbon atoms.
  • the washing agent cakes of the invention contain from about 12% to 47% preferably from 18% to 40% by weight of superfatting agents melting at temperatures of from 30 to 80C, preferably from 40 to 70C.
  • superfatting agents melting at temperatures of from 30 to 80C, preferably from 40 to 70C.
  • These are preferably fatty acids having from 10 to carbon atoms and an iodine number below 10, fatty alcohols having from 10 to 20 carbon atoms and an iodine number below 10, mono-, dior triglycerides of the above fatty acids, esters of the above fatty acids with the above fatty alcohols, lanolin, vaseline, the citric acid-difatty alcohol pentaerythritol difatty acid esterification product and mixtures of the above.
  • nonionic ethylene derivatives fatty acid alkylolamides, and amphoteric tensides possess skin-pleasing properties. If such tensides are incorporated into the shaped washing agents, according to the invention, they can at the same time partially take the role of a superfatting agent.
  • superfatting agents are products which differ from the above described nonionic alkylene oxide derivatives only in those that have an alkoxylation degree which is incomplete for water solubility.
  • water-insoluble propylene oxide derivatives or ethoxylation products optionally containing propylene and/or butyleneglycol radicals, in which the amount of the added ethylene oxide is insufficient for the water insolubility.
  • water-insoluble nonionic compounds are, for instance, commercially available under the name Ucon Fluid.
  • water-soluble or water-insoluble dyes may be present.
  • the water-insoluble dyes include here also the color pigments frequently used for the brightening of washing agent cakes. Besides such washing agent cakes may contain brighteners, particularly in case of white washing agent cakes.
  • organic complexing agents can be added, and in addition frequently the incorporation of dirt carriers has proven useful.
  • the usable brighteners are mostly, if not exclusively, derivatives of the diaminostilbene sulfonic acid of the diarylpyrazolines, and of aminocoumarin.
  • Examples for brighteners from the class of the diaminostilbenesulfonic acid are compounds according to formula I:
  • R and R may be halogen atoms, alkoxyl groups, the amino group or radicals of aliphatic, aromatic or heterocyclic primary or secondary amines, as well as radicals of aminosulfonic acids, whereby the aliphatic radicals present in the above groups contain preferably 1 to 4, and particularly 2 to 4 carbon atoms, while the heterocyclic ring systems are mainly 5- or 6- membered rings.
  • aromatic amines preferably radicals of aniline, anthranilic acid or aniline sulfonic acid are used. Brighteners derived from diaminostilbene sulfonic acid are used mainly for cotton.
  • R is the radical NHC H and R can be the following radicals: NH NHCH ,-N- HCH CH OH,-NHCH CH -OCH .N- I-ICH CH CH OCH I CH3-N-CH2-CH2OH.
  • R and R are hydrogen atoms, possibly alkyl or aryl radicals substituted by carboxyl-, carbamide-, or ester groups
  • R and R are hydrogen or short chain alkyl radicals
  • Ar and Ar are aryl radicals, such as, phenyl, diphenyl, or naphthyl and may have other substituents, such as, hydroxy-, alkoxy-, hydroxyalkyl-, amino-, alkylamino-, acylamino-, carboxyl-, carboxylic ester-, sulfonic acid-, sulfonamide-, and sulfonic groups, or halogen atoms.
  • polyamide brighteners belong also aliphatic or aromatic substituted aminocoumarins, for example, the 4-methyl-7-dimethylamino-, or the 4-methyl-7- diethylaminocoumarin.
  • polyamide brighteners are the compounds l-(benzimidazolyl-2)- 2-(N-hydroxyethyl-benzimidazolyl-Z)-ethylene and 1-N-ethyl-3-phenyl-7-diethylaminocarbostyril.
  • Suitable brighteners for polyester and polyamide fibers are the compounds 2,5-di-(benzoxazolyl-2')-thiophene and 1,2-di-(5 '-methyl-benzoxazolyl-2')-ethylene.
  • the brighteners together with other ingredients of the invention products, are present as aqueous solutions or as pastes, and are converted into solids by heat drying, it is recommended to add organic complexing agents as stabilizers for the brighteners in amounts ofat least 0.1% preferably 0.2 to 1% by weight of the solid products.
  • organic complexing agents belong, for instance, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid,
  • R is alkyl and R is alkylene, both with 1 to 8, preferably 1 to 4 carbon atoms
  • X and Y are hydrogen or alkyl with 1 to 4 carbon atoms
  • Z is the groups -OI-I,NH or -NXR.
  • methylenediphosphonic acid 1 -hydroxyethane-1 ,1 -diphosphonic acid, 1- aminoethane-l,l-diphosphonic acid, amino-tri-(methylenephosphonic acid) methylamino or ethylaminodi-(methylenephosphonic acid) as well as ethylene diamine-tetra-(methylenephosphonic acid). All these complexing agents can be present as free acids, preferably as alkali metal salts.
  • watersoluble colloids mostly organic, are suitable, such as the water-soluble salts of polymeric carboxylic acids, glue, gelatine, salts of ether-carboxylic acids or ethersulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • watersoluble polyamides, containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above named starch products can be used, such as degraded starch, aldehyde starch, gelatinized starch, etc.
  • polyvinylpyrrolidone is usable.
  • non-tenside addition products are preferably charged by weight of the total composition.
  • the shaped washing agents are prepared in a conventional manner.
  • the power necessary for the processing of the mass on rolls, in extruding presses, and in converting of the crude shaped pieces to the desired form can be changed by the water content of the mass. If, for the processing of a special mixture, a too large power expenditure should be required, the latter can be decreased by increasing the water content. In this event, the claimed upper limit of the water content can be surpassed however on storing the pieces dry and thus attain after some time the claimed water content.
  • This olefin mixture had been prepared by sulfonation of 1 mol of olefin with about 1.2 mols of gaseous sulfur trioxide, diluted with inert gas, hydrolysis of the crude: sulfonation product with the calculated amount of aqueous sodium hydroxide at temperatures of about 100C and bleaching of the sulfonate with the aid of hypochlorite.
  • the mixture of the two sulfonates contained about 5% by weight of neutral salts (Na SO and NaCl), based on the anhydrous sulfonate mixture.
  • the mixed citric acid ester mentioned in the examples was an esterification product of one mol of citric acid tallow fatty alcohol-diester and one mol of pentaerythritol-coconut fatty acid diester.
  • the ingredients in the given amounts were mixed in a kneader at temperatures of 60 to C, brought to the requried water content, homogenized on rolls and then extruded from vacuum extruders: in a strand of the cross-section of the customary commercial toilet-soap cakes. By cutting and pressing of these strands, products of the desired shape and size were obtained.
  • the detergent cakes were prepared from the composition given in the examples, whereby the quantitative data for the olefin sulfonate and the sulfosuccinic acid ester refer to the anhydrous technical product, i.e., they include neutral salts and unsulfonated olefin as well as unreacted fatty alcohol (about 1%).
  • the foam formed during washing is similar to that of soap both in its structure and in its behavior.
  • the foam present in the wash basin collapses quickly on rinsing.
  • the abrading observed in washing is largely identical to that of good toilet soap. People who wash or bathe with these cakes did not observe a disagreeable degreasing of the skin.
  • builders is also used in the field of the detergent powders, where it means certain water soluble substances enhancing the washing action of detergents. In this case, however, the term builders designates a certain kind of water insoluble substances, usualy incorporated into soap pieces to improve their body properties when in contact with water.
  • Shaped washing agents based on synthetic detergents having a composition consisting essentially of (A) from 55% to 80% by weight of a tenside mixture consisting essentially of I) from 70% to 100% by weight of said tenside mixture of a sulfonate mixture consisting essentially of (a) from 20% to 70% by weight of said sulfonate mixture ofa water-soluble salt ofa monoester of a sulfodicarboxylic acid selected from the group consisting of sulfoalkanedioic acids having 3 to 8 carbon atoms and sulfobenzenedicarboxylic acids, monoesterified with fatty alcohols having 8 to 18 carbon atoms, at least 50% of said fatty alcohols having 10 to 16 carbon atoms and (b) from 30% to 80% by weight of said sulfonate mixture of a water-soluble salt of a mixture of hydroxyalkane sulfonates, alkene sulfonates and alkane disulfonates
  • Shaped washing agents based on synthetic detergents having a composition consisting essentially of(A) from 55% to 80% by weight of a tenside mixture consisting essentially of (I) from to 100% by weight of said tenside mixture ofa sulfonate mixture consisting essentially of (a) from 20% to 70% by weight of said sulfonate mixture of an alkali metal salt ofa monoester of sulfosuccinic acid monoesterified with a primary alkanol having 12 to 14 carbon atoms and (b) from 30% to by weight of said sulfonate mixture of an alkali metal salt of a mixture of hydroxyalkane sulfonates, alkene sulfonates and alkane disulfonates, the individual components of said alkali metal salt of a mixture of sulfonates having from 12 to 16 carbon atoms, and (2) from 0 to 30% by weight of said tenside mixture of tensides excepting said (a) and (b) selected

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
US306014A 1969-10-01 1972-11-13 Shaped washing agents based on synthetic tensides Expired - Lifetime US3862965A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE756790D BE756790A (fr) 1969-10-01 Detergent faconne a base de surfactifs synthetiques
DE19691949562 DE1949562B2 (de) 1969-10-01 1969-10-01 Geformte waschmittel auf basis synthetischer tenside
NL7013063.A NL164602C (nl) 1969-10-01 1970-09-03 Gevormd wasmiddel.
FR707035096A FR2064076B1 (enrdf_load_stackoverflow) 1969-10-01 1970-09-29
AT884070A AT301726B (de) 1969-10-01 1970-09-30 Geformte Waschmittel auf Basis synthetischer Tenside
US306014A US3862965A (en) 1969-10-01 1972-11-13 Shaped washing agents based on synthetic tensides

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19691949562 DE1949562B2 (de) 1969-10-01 1969-10-01 Geformte waschmittel auf basis synthetischer tenside
US7620370A 1970-09-28 1970-09-28
US306014A US3862965A (en) 1969-10-01 1972-11-13 Shaped washing agents based on synthetic tensides

Publications (1)

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US3862965A true US3862965A (en) 1975-01-28

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US306014A Expired - Lifetime US3862965A (en) 1969-10-01 1972-11-13 Shaped washing agents based on synthetic tensides

Country Status (6)

Country Link
US (1) US3862965A (enrdf_load_stackoverflow)
AT (1) AT301726B (enrdf_load_stackoverflow)
BE (1) BE756790A (enrdf_load_stackoverflow)
DE (1) DE1949562B2 (enrdf_load_stackoverflow)
FR (1) FR2064076B1 (enrdf_load_stackoverflow)
NL (1) NL164602C (enrdf_load_stackoverflow)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962150A (en) * 1974-04-10 1976-06-08 Richardson-Merrell Inc. Foam producing cleansing compositions
US3968047A (en) * 1973-03-01 1976-07-06 Citrex, Societe Anonyme Detergent compositions
US3968046A (en) * 1973-03-01 1976-07-06 Citrex, Societe Anonyme Polyphosphate free detergent compositions
WO1980002154A1 (en) * 1979-04-09 1980-10-16 Gaf Corp Detergent bar composition and binder therefor
US4335025A (en) * 1980-02-19 1982-06-15 Witco Chemical Corporation Process for the preparation of synthetic detergent bars, and products produced thereby
US4647394A (en) * 1981-04-07 1987-03-03 Mitsubishi Chemical Industries Limited Soap composition
US5543072A (en) * 1992-10-05 1996-08-06 Mona Industries, Inc. Synthetic detergent bars and method of making the same
US5620949A (en) * 1995-12-13 1997-04-15 The Lubrizol Corporation Condensation products of alkylphenols and aldehydes, and derivatives thereof
US20130239313A1 (en) * 2010-11-12 2013-09-19 Henkel Ag & Co. Kgaa Ball-shaped toilet blocks based on anionic surfactants

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3707035A1 (de) * 1987-03-05 1988-09-15 Henkel Kgaa Geformte reinigungsmittel

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3224976A (en) * 1960-05-20 1965-12-21 Colgate Palmolive Co Detergent bar
US3247121A (en) * 1962-04-30 1966-04-19 Procter & Gamble Washing composition
US3312627A (en) * 1965-09-03 1967-04-04 Procter & Gamble Toilet bar
US3523089A (en) * 1966-03-18 1970-08-04 Lever Brothers Ltd Toilet bar
US3629127A (en) * 1968-08-05 1971-12-21 Basf Wyandotte Corp Low foaming rinse additive
US3640882A (en) * 1969-05-01 1972-02-08 Continental Oil Co Sulfosuccinate half ester lime soap dispersing agents
US3705114A (en) * 1971-06-16 1972-12-05 Chevron Res Hydrogenated olefin

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3224976A (en) * 1960-05-20 1965-12-21 Colgate Palmolive Co Detergent bar
US3247121A (en) * 1962-04-30 1966-04-19 Procter & Gamble Washing composition
US3312627A (en) * 1965-09-03 1967-04-04 Procter & Gamble Toilet bar
US3523089A (en) * 1966-03-18 1970-08-04 Lever Brothers Ltd Toilet bar
US3629127A (en) * 1968-08-05 1971-12-21 Basf Wyandotte Corp Low foaming rinse additive
US3640882A (en) * 1969-05-01 1972-02-08 Continental Oil Co Sulfosuccinate half ester lime soap dispersing agents
US3705114A (en) * 1971-06-16 1972-12-05 Chevron Res Hydrogenated olefin

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3968047A (en) * 1973-03-01 1976-07-06 Citrex, Societe Anonyme Detergent compositions
US3968046A (en) * 1973-03-01 1976-07-06 Citrex, Societe Anonyme Polyphosphate free detergent compositions
US3962150A (en) * 1974-04-10 1976-06-08 Richardson-Merrell Inc. Foam producing cleansing compositions
WO1980002154A1 (en) * 1979-04-09 1980-10-16 Gaf Corp Detergent bar composition and binder therefor
US4234464A (en) * 1979-04-09 1980-11-18 Gaf Corporation Detergent bar composition and binder therefor
US4335025A (en) * 1980-02-19 1982-06-15 Witco Chemical Corporation Process for the preparation of synthetic detergent bars, and products produced thereby
US4647394A (en) * 1981-04-07 1987-03-03 Mitsubishi Chemical Industries Limited Soap composition
US5543072A (en) * 1992-10-05 1996-08-06 Mona Industries, Inc. Synthetic detergent bars and method of making the same
US5620949A (en) * 1995-12-13 1997-04-15 The Lubrizol Corporation Condensation products of alkylphenols and aldehydes, and derivatives thereof
US20130239313A1 (en) * 2010-11-12 2013-09-19 Henkel Ag & Co. Kgaa Ball-shaped toilet blocks based on anionic surfactants

Also Published As

Publication number Publication date
DE1949562A1 (de) 1971-04-15
FR2064076B1 (enrdf_load_stackoverflow) 1973-01-12
DE1949562C3 (enrdf_load_stackoverflow) 1978-08-24
NL164602C (nl) 1981-01-15
NL7013063A (enrdf_load_stackoverflow) 1971-04-05
DE1949562B2 (de) 1977-12-22
AT301726B (de) 1972-09-11
FR2064076A1 (enrdf_load_stackoverflow) 1971-07-16
BE756790A (fr) 1971-03-29

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